Synthesis and Studies of Magnetic Layered Host-Guest Materials

9311597 Nocera这项提议的动机是合理设计磁性物质的挑战。这项研究将利用层状材料中的结构控制来研究分子相互作用和磁耦合之间的相互作用。磷酸盐层状主体的晶内环境将提供脚手架，使有机无机插层剂与层和彼此之间具有明确的关系。通过氧化还原插层和离子交换插层的方法合成层状磷酸盐和磷酸盐主体的磁性插层。插入特殊设计的等结构有机和无机顺磁性或抗磁性客体将允许探测层内、层-客体、客体-客体和更高阶磁相互作用。在顺磁性插入物的情况下，开壳轨道的形状和相对于层的排列的作用可以结合图库中的探索方向来评估。最后，概述了组装顺磁探测的磁性主体层的探索路径。随着这项提议解决磁性耦合的结构问题，具有磁性定制特性的材料的合理设计的新策略将会出现。此外，在层状磁性材料合成程序中整合的结构-磁性关联将为新的磁性预测结构理论的发展提供动力。虽然拟议工作的主要重点是合成，但根据需要，将在与该大学凝聚态物理小组的既定合作范围内开发机械模型。***

9311597 Nocera This proposal is motivated by the challenge of rationally designing magnetic substances. This research will exploit the structural control available in layered materials to study the interplay between molecular interactions and magnetic coupling. The intracrystalline environments of phosphate layered hosts will provide the scaffolding to position organic inorganic intercalants in well-defined relationships to the layers and to each other. Magnetic intercalates of layered phosphate and phosphonate hosts will be synthesized by redox and ion-exchange intercalation methods. Insertion of specially designed isostructural organic and inorganic sets of para- or diamagnetic guests will permit the probe of intralayer, layer-guest, guest-guest, and higher order magnetic interactions. In the case of paramagnetic intercalants, the roles of the open-shell orbitals' shape and alignment relative to the layers can be assessed in connection with quest orientation within the galleries. Finally, an exploratory path is outlined to assemble magnetic host layers about paramagnetic quests. As this proposal addresses structural issues of magnetic coupling, new strategies for the rational design of materials with magnetically tailored properties will emerge. Additionally, the structure- magnetism correlations assembled in this layered magnetic materials synthesis program will provide impetus for the development of new predictive structural theories of magnetism. Although the primary focus of the proposed work is synthetic, development of mechanistic models will be pursued as needed within an established collaboration with the condensed matter physics group at the University. ***